JPS6333478A - Novel composition based on indanthrene blue pigment - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to compositions containing indanthrone blue pigments and sulfonated indanthrone blue derivatives, and their use for the coloring of polymeric organic materials.

Indanthrone blue pigments have been known for some time. Japanese Patent Publication No. 1707/1983 describes that the solvent resistance of indanthrone blue can be improved by adding 30% by weight of sulfonated copper phthalocyanine to indanthrone blue as a base.

However, from U.S. Pat. No. 4,310,359, it is learned that by incorporating into a pigment a pigment compound obtained by introducing a substituent such as a sulfo group, a sulfonamido group, an aminomethyl group or a phthalimidomethyl group into an organic pigment, or It is known that the effects obtained by incorporating alkaline earth metal sulfonates or organic amine salts of zo dyes into azo compounds, particularly non-aggregation and crystal stability, are insufficient. And in the same patent specification, the color index (C, 1,) Pigment Red 1
It has been proposed to improve the rheological properties of certain pigments, including 77, by incorporating them with pigments that have been modified by introducing one or more aminosulfonamide groups.

In contrast to the teachings of the above-mentioned US patent documents, it is quite surprising that according to the present invention the addition of sulfonated indanthrone blue derivatives to indanthrone blue pigments makes it possible to achieve fully satisfactory rheological properties of the product. It was found that it was improved to a certain degree.

That is, the composition provided by the present invention comprises a) Carpenter's Indanthrone Blue pigment and b) Formula II? , HaN e(R)(R1)(R2)(R3) e
'XL taste (Ni), M is a monovalent, divalent or trivalent metal cation, n is a number of 1.2 or 3, R, R,, R2
, R3 are each independently hydrogen, C1-C18-
Alkyl, Cs -C6-cycloalkyl, phenyl,
or phenyl substituted by Cl-C18-alkyl, or R2 and R3 together with the nitrogen atom to which they are attached represent a pyrrolidine, imidazolidine, piperidine, piperazine or morpholine group. or R1, R2, R3 together with the nitrogen atom to which they are bonded mean a pyrrole group, a pyridine group, a picoline group, a pyrazine group, a quinoline group or an inquinoline group), and m is The composition contains a sulfonated indanthrone blue derivative with a numerical value of 0.5 to 2.

xe is preferably He, and most preferably the formula ? It is the basis of

Examples of groups of the formula xe are alkali metal cations, alkaline earth metal cations, aluminum cations or transition metal cations, f, and yt4fNae, Ke,
Mg2e, Ca2@, Sr2@, B
a2 e , Mn2 e , C112@ ,
N i 2 @ , (: d 2 @
, (: 03 @ , AI"' and Cr
It is 5e. However, preferably an alkali metal cation or an alkaline earth metal cation (n = 1 or 2)
and Nae and Ca2e are most preferred.

Examples of Cl-C18-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, 5ee-butyl,
tert-butyl, n-pentyl, tert-pentyl, hexyl, heptyl, octyl, decyl, dodecyl,
Tetradecyl, hexadecyl, heptadecyl or octadecyl.

An example of C5-C6-cycloalkyl for R, R,, R2, R3 is cyclopentyl or preferably cyclohexyl.

R, R1, R2, R3 as phenyl substituted with ct-C18-alkyl is preferably CI2-CR8
- phenyl substituted with alkyl.

Na (R) (R1) (R2) (R3) (7) Examples can be mentioned below: NeH4, NeR3CH
3, NeR2(CH3)2, NeR3C2R5, Ne
R2(C2R5)2 , NeR3C3H7-iso,
Na R3-cyclohexyl, Na R2-(cyclohexyl)2, NeR2(CH3)(C6Hs), N
eR3C6R5, NeR3-p-octadecylpheny,
and Ne(CH3)a.

m is preferably l.

The sulfonated indanthrone blue component (b) can be produced by a method known per se. For example, fuming sulfuric acid, in the presence or absence of a catalyst such as boric acid,
sulfonation with sulfuric acid or liquid sulfur trioxide (see DE 216 891) and optionally in a further step with a salt of the desired metal, such as an acetate, chloride, nitrate or sulphate. or by reaction with one of the appropriate amines. The concentration of sulfonating agent and reaction conditions are closely dependent on the number of sulfonic acid groups desired to be introduced into the indanthrone blue molecule.

The compositions of the invention can be prepared by mixing each indanthrone blue component (a) and (b) in the desired ratio or by partially sulfonating and then reacting with a metal salt or amine as described above. can be manufactured.

The proportions of the components in the composition of the invention can be chosen freely. However, the preferred ratio is component (b) 0.2 to 1000% by weight: component (a) 99.8 to 90% by weight,
The most preferred ratio is component (b) 2.0 to 6.0% by weight.
: 98.0 to 94% by weight of component (a).

The addition of component (b) can be carried out before or after conditioning the pigment. Conditioning here refers to, for example, precipitation in an alkaline medium (silicification), precipitation in sulfuric acid, dry milling in the presence or absence of salt, solvent or wet milling. It is meant to prepare indanthrone blue in a finely divided form by grinding or cross-mixing, preferably in the presence of salt.

Depending on the method of conditioning or end use, it may be advantageous, in addition to the addition of sulfonated indanthrone blue, to also add certain amounts of texture improvers to the pigment before or after conditioning. Suitable texture improving agents are particularly exemplified by fatty acids having not less than 18 carbon atoms, such as stearic acid or behenic acid or their amides or metal salts, preferably magnesium salts, as well as plasticizers, waxes, resin acids such as abietin. acids, colophonium soaps, alkylphenols, or aliphatic alcohols such as stearyl alcohol or vicinal diols such as dodecane-1,2-diol, and modified colophonium/maleate resins or fumaric acid/colophonium resins. ! The texture improver is preferably added in an amount of 0.1 to 30% by weight, most preferably 2 to 15% by weight, based on the final product.

The compositions of the invention are suitable as pigments for coloring polymeric organic materials.

Examples of polymeric organic materials that can be colored or pigmented in the compositions of the invention include: cellulose ethers and esters such as ethylcellulose, nitrocellulose, cellulose acetate,
Cellulose acetate, natural or synthetic resins such as polymeric or condensed resins, such as aminoplasts, especially urea/formaldehyde resins and melamine/formaldehyde resins, alkyd resins, phenolic plastics, polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides , polyurethanes, polyesters, rubbers, casein, silicones and silicone resins, which can be used alone or in mixtures.

The polymeric compounds exemplified above can be used alone or in mixtures in the form of plastics, melts or spinning solutions, varnishes, paints, printing inks. Depending on the application, it may be advantageous to use the pigments in the form of toners or preparations. used.

The coloring or coloring of polymeric organic materials with the composition of IJI can be achieved, for example, by incorporating the composition, optionally in the form of a masterbatch, into the substrate to be colored using a roll mill, mixer or attritor. Implemented by.

The colored material is then processed into the desired final shape by methods known per se, such as calendering, molding, extrusion, coating, spinning, casting, injection molding, etc. It is often desirable to incorporate plasticizers into the polymer compound before processing in order to produce crack-free moldings or to reduce the brittleness of the moldings; suitable plasticizers include, for example, phosphoric acid, It is an ester of phthalic acid or sebacic acid. The incorporation of plasticizers can be carried out before or after incorporating the composition into the polymer. In addition to the composition of the invention, fillers or other color-forming ingredients, such as white, colored or A black pigment can also be added to the polymeric organic compound in any amount.

When coloring varnishes and printing inks, the polymeric organic material and the composition of the invention may be combined with optional additives such as fillers,
Finely dispersed or dissolved in common organic solvents or solvent mixtures together with other pigments, desiccants or plasticizers, etc. This operation can be carried out individually or by finely dispersing or dissolving several components in a solvent. And then mix all the ingredients.

The color fastness of, for example, plastics, filaments, varnishes or printed materials obtained using the compositions of the invention is generally excellent. That is, for example, it has good dispersibility, high transparency, and is suitable for over-spraying, migration, heat,
It has excellent light fastness and weather resistance.

Furthermore, compared to non-sulfonated indanthrone blue, the compositions of the invention have greater tinting strength and improved rheological properties, especially in varnishes and printing inks, and when used simultaneously with white pigments. Floating spots (
There are fewer separation phenomena such as floating out, reduced tendency to agglomeration, and high color gloss of the final product.

Since the pigment composition of the present invention has excellent rheological properties, it is possible to produce a varnish containing pigment at a higher concentration than before.

The composition of the invention comprises aqueous and/or solvent-based varnishes,
It is particularly suitable for coloring automotive varnishes.

Hereinafter, the present invention will be further explained by examples.

Length 10I diameter 1.2cm + 7) Steel ball 1500g, 150g
, aluminum sulfate 16)! 20 r3sg, 15g of crude indanthrone blue, West German Patent No. 216891
A steel vessel is charged with 0.75 g of indanthrone blue sulfonic acid (m=1) prepared by the method described in the patent specification and 3.2 ml of cyclohexanol. The container is closed and placed on a roller bed and rotated for 72 hours. After this, the steel balls and nails are separated from the milling material, the milled material is placed in 500 ml of water containing 2.5 ml of concentrated sulfuric acid, and the pigment suspension is stirred for 2 hours at 80-90.degree. The pigment is separated by filtration at 30°C, the filter cake is washed with water to remove salts, dried under vacuum at 80°C and powdered.

The blue pigments thus obtained, when incorporated into varnishes, give a very intense coloring with high chroma.

Shihai Huang λ 10 g of crude indanthrone blue and 0.3 g of indanthrone blue sulfone fi (m = 1) were mixed with 60% concentrated sulfuric acid.
Stir in m1 at room temperature for 2 hours. Add this mixture to 4
Drop onto ice water at a temperature below °C. Add this 2 more times
Stir at 80° C. for an hour, filter and wash the IIa filter cake to neutrality. Next, I bought this filter cake for 200+*
1 of water and heat the suspension to 70°C. After this, 1.0 g of dodecane-1,2-diol is added and the mixture is stirred at 70° C. for 30 minutes.

Cool to 30°C and filter. The filter cake is washed with water and dried at 80°C. A blue pigment is thus obtained. This pigment is ideal for coloring varnishes, giving high tinting strength, excellent gloss, high chroma and the colors have good fastness.

1 ml 27 g of crude indanthrone blue, 0.7 g of indanthrone blue sulfonic acid (m=1), 3.7 g of hydrogenated abietic acid.

130 g of NaCl and 44 g of diacetone alcohol
1 into a 5001 experimental kneader. This mixture is kneaded for 6 hours without cooling. The temperature rises to 40°C. Add this concentrate to 2 cups of water and stir for 3 hours. The pigment is isolated by filtration, the filter cake is washed free of salt with water, dried at 80° C. and ground. The blue pigment thus obtained is ideal for mixing into plastics and varnishes, gives high tinting strength and high chroma, and the color has good fastness. The varnishes produced thereby have excellent rheological properties and show no tendency to agglomerate.

Support 1 The operation was carried out in the same manner as in Example 3. However, this time, the amount of indanthrone blue sulfonic acid was changed from 0.7g to 1.4g.
Changed to. The blue pigment obtained likewise had good coloring properties and exhibited better rheological properties.

The operation was carried out in the same manner as in Example 3. However, this time, the amount of indanthrone blue sulfonic acid was changed from 0.7g to 2.4g.
Changed to. The blue pigment obtained likewise had good coloring properties and exhibited better rheological properties.

Support 1 The operation was carried out in the same manner as in Example 3. However, this time, Na
N a Cl (7) 120 instead of 130 g of C1
A mixture of 15 g and 15 g of CaCl2 was used. The resulting indanthrone blue pigment contained about 2.7% of the calcium salt of indanthrone blue sulfonic acid and had good pigment properties similar to those of Example 3.

11) The same operation as in Example 3 was carried out. However, this time, instead of 130g of NaC1, 1 of NaC1
A mixture of 20 g and 10 g of aluminum sulfate was used. The resulting indanthrone blue pigment contained about 2.7% of the aluminum salt of indanthrone blue sulfonic acid and had good pigment properties similar to those of Example 3.

Branch IJ The operation was carried out in the same manner as in Example 4. However, this time, instead of 130g of NaC1, NaC1
(7) A mixture of 120 g and 10 g of 5rC1z was used. The resulting indanthrone blue pigment has a pigment of approx.
It contained 5% of the Sr salt of indanthrone blue sulfonic acid and had the same good pigment properties as the previous one.

The same operation as in Example 3 was carried out for the first stitch. However, this time, instead of 130g of NaCl, NaCl
(7) A mixture of 120 g and 10 g of BaClz was used. The resulting indanthrone blue pigment is approximately 5
．． It contained 5% barium salt of indanthrone blue sulfonic acid and had good pigment properties similar to those of Example 3.

The operation was carried out in the same manner as in Wataru Maruwa Uni Example 4. However, this time, instead of 130g of NaC1, 1 of NaC1
A mixture of 20 g and 15 g of MgC1z was used. The resulting indanthrone blue pigment contained about 5.5% of the magnesium salt of indanthrone blue sulfonic acid and had the same good pigment properties as those described above.

27.5 g of crude indanthrone blue, 3.7 g of hydrogenated abietic acid, 130 g of NaCl and 44 ml of diacetone alcohol are charged to a 500 ml laboratory kneader.

The mixture is mixed for 6 hours without external cooling. The temperature rises to 40°C during this time. 2 of this concentrate! Add to L of water and stir for 3 hours.

The pigment is isolated by filtration, the filter cake is washed free of salt and resuspended in 300 ml of water. The suspension is heated to 70° C. and then 1.4 g of the sodium salt of indanthrone blue sulfonic acid are added (m=1
), and the mixture is stirred for 30 minutes at 70°C. 3
After cooling to 0°C, the pigment was isolated by filtration, washed with water,
Dry at 80°C and grind. The resulting blue pigment exhibits excellent rheological properties when incorporated into varnishes, has high tinting strength and chroma, and has excellent weather resistance. When incorporated into plastics, the pigments exhibit good dispersibility.

The same procedure as in Example 11 was carried out except that the addition of 3.7 g of Shibai-1 hydrogenated abietic acid was omitted. This blue pigment has excellent rheological properties and shows little tendency to agglomerate when incorporated into varnishes.

13.5 g of crude indantron blue was placed in a 5001 glass bead mill with a diameter of 8 cm.

1.5 g of hydrogenated abietic acid fine powder, 0.7 g of sodium salt of indanthrone blue sulfonic acid (m=1), 125 g of water, 400 glass beads with a diameter of 3.5 to 4.0 mm.
Load g. Do not externally cool this batch.
Stir for 12 hours at a speed of rpm. The rotation speed of the metal paddle stirrer with a diameter of 5.5 cm is 0.92 m/sec. The glass beads are separated from the pigment suspension, washed with water and filtered.

Dry the pigment at 80°C. Therefore, blue pigment 1 containing about 4% of indanthrone blue sulfonic acid sodium salt
3.5 g is obtained.

When used in varnishes, this pigment gives a highly saturated, very intense coloration and good fastness properties and shows no tendency to agglomeration.

1. Water 100g and ethylene glycol 2 instead of 125g water
The operation was carried out in the same manner as in Example 13, except that a mixture with 5 g was used.

The resulting pigment likewise had excellent coloring properties and very good dispersibility.

Branch 1 Group 1 27g of crude indanthrone blue, 130g of NaCl
441 g of diacetone alcohol and diacetone alcohol are loaded into a 500 μl laboratory kneader. This mixture is kneaded for 6 and a half hours with external cooling with water. Add this concentrate to 2 cups of water and stir for 3 hours. The pigment is isolated by filtration and washed free of salts. The wet filter cake was resuspended in 400 liters of water and to this suspension was added the n-butylammonium salt of indanthrone blue sulfate obtained by reaction of indanthrone blue sulfuric acid with n-butylamine (m=1). (m=l) 1.4g and laurylamine 0.6g
and add. The batch is heated to 80°C, stirred at 80°C for 30 minutes, then cooled to 20°C. The pigment was isolated by filtration and the filter cake was washed at 80°C.
Dry and grind in a . The pigments thus obtained, when incorporated into varnishes, have high tinting strength, exhibit no tendency to agglomerate and give blue colors of high chroma.

Shimugoyu J 150 g of water, 9 g of 50% solution of sodium hydroxide, 1.2 g of hydrogenated abietic acid and 1 portion of sodium dithionate
．． To 2 g of the mixture are added 15 g of leuco danthrone in the form of a wet filter cake. After adding 220 g of glass beads (diameter 1 mm), this aqueous suspension of leuco danthrone was heated at a temperature of 25 to 30°C using a high-speed impeller with air allowed to flow in at about 200 Or
Stir at a rotational speed of pm. The pigment suspension is then separated from the beads and washed with 3001 water. The combined suspension is adjusted to 0 with dilute hydrochloric acid.

The pigment is isolated by filtration, washed with water and resuspended in 200 ml of water. This suspension was added to indanthrone blue sulfate (
Add 0.75 g of the sodium salt of m=1). This is heated to 70°C, stirred at 70°C for 30 minutes, and then cooled to 25°C. i! ! isolate the pigment by
The filter cake is washed with water and dried at 80°C. When incorporated into varnishes, this powdered pigment gives a very intense blue color with good fastness.

Branch 1 The operation was carried out in the same manner as in Example 15. However, this time, 2.0 g of ammonium salt of indanthrone blue sulfonic acid was used instead of 1.4 g of n-butylammonium salt. Pigments with likewise excellent properties were obtained.

Strut 5±1 The operation was carried out in the same manner as in Example 17. However, this time, 2.0g of ammonium salt of indanthrone blue sulfonic acid
311-8 g of tetramethylammonium was used instead. Pigments with likewise excellent properties were obtained.

Group 11 J The operation was carried out in the same manner as in Example 17. However, this time, 2.0g of ammonium salt of indanthrone blue sulfonic acid
N,N-dimethylphenylammonium salt (m
=0.5) 3.6g was used. A dye with similarly excellent properties was obtained.

Shibaoka The operation was carried out in the same manner as in Sub-Example 7. However, this time, indanthrone blue sulfonic acid (m=2) was used. Pigments with likewise excellent properties were obtained.

Length Ju1ヱ''2 The same operation as in Example 4 was carried out. However, this time the amount of hydrogenated abietic acid was changed from 3.7g to 0.9g. A pigment with excellent properties was obtained.

A mixture of 130 parts of Yusteatite beads (diameter 8 mm) and 47.5 parts of a thermosetting acrylic resin varnish having the following composition was loaded into a 200 l glass bottle with a twist stopper and placed on a roll gear bed. Dispersed for 72 hours.

Acrylic resin varnish composition: 7') I771/ (VIACRYL) ■VC
3737 Ri) Le resin, 80! (Manufacturer: Pierzba Kainstharz) 41.3 parts MAPRENAL TTx melamine resin, 55% (Manufacturer: Hoechst) 16.3 parts Xylene 32.8 parts Ethyl glycol acetate
4.6 parts Butyl acetate 2.0 parts Silicone oil A■, 1% xylene solution (manufacturer: Bayer) 1.0 parts Indanthrone blue mixture obtained in Example 1
After dispersing 2.5 parts for 72 hours, the steatite beads were taken out, and the following substances were thoroughly mixed into 8.0 parts of the obtained master mixture: ALCOA ■ Aluminum paste (aluminum content 60-65%, Manufacturer: Aluminum Corporation of America)
0.6 parts methyl ethyl ketone i, o parts 18.4 parts of the above thermosetting acrylic varnish.

The resulting mixture was spray coated onto an aluminum plate and then baked at 130° C. for 30 minutes. A very intense blue metallic paint was obtained whose fastness was excellent.

Similarly excellent finished paints were obtained when any of the pigments of Examples 2 to 16 were used in place of the pigment of Example 1.

A mixture of 130 g of steatite balls (8 mm in diameter) and 47.5 g of varnish and the indanthrone blue pigment obtained in Example 3 was used for alkyd/melamine baking with the following composition:
．． A mixture of 5 g and
Spread out time.

Varnish composition: Beckoso I ■27-320 (
Reichhold Chemical Company) 60% xylene solution 60g Super-Beckamin 013-50
1 (Reichhold φ Chemical Co.) 50% solution in xylene/butanol 2:l mixture
36g xylene
After dispersing 2 g of ethylene glycol monomethyl ether for 120 hours, the glass beads were separated and removed.
2.4 g of this dispersed master mixture was added to titanium dioxide Kronos RN59 (Kronos Titan Gs+bH) 6
0 g and a further 24.0 g of the alkyd/melamine stoving were mixed with the varnish.

The resulting colored varnish solution was spray applied onto an aluminum plate, which was then baked at 130° C. for 30 minutes. A very strong blue finish with excellent fastness was thus obtained.

Back groove” Lζ1 Steatite beads (diameter 8 mm) 130 parts Alkyd varnish-based ALFTALAT AC451M■, solid content 6
0% (manufactured by Hoechst) 24.5 parts Xylene 18.7 parts Mixture of indanthrone blue pigment obtained in Example 21
4. Twist the mixture containing 3 parts into a 20-liter bottle with a stopcock.
It was loaded into a 0ml glass flask and dispersed on a roller gear bed for 72 hours. The steatite balls were then removed.

A millbase was thus obtained containing 9% by weight of pigment, 40.5% by weight of total solids, and a pigment/binder ratio of 0.3. The flow characteristics of this mill base were determined by the Hague (
HAAKE) Viscometer [Rotov: 1 (Rotov)
isco)■RV12: Measurement temperature 25℃: Measurement system 5V-3r; Shear range D=0-100 [+/sl
). For a simple characterization of the flow curve, D=IO[1/s
Just look at the viscosity values at l and 100 [1/s].

The viscosity values measured for the millbase containing the pigment mixture of Example 21 are as follows: D = l G [177 mPa at 1/sl
-5D = 100 [+/127 m at sl
Only indanthrone blue as Pa-5 pigment (without addition of sodium salt of indanthrone blue sulfonic acid)
The viscosity values measured for the millbase containing 20 = 10 [+/12 at sl
At 74 mPa-5D = 100 [+/s] 211 mPa-5 heat m Indanthrone blue pigment mixture 1 obtained in Example 4
．． 0g, antioxidant [IRGANOX 1010 from Civer Geigi], Og and high density polyethylene granules [Hüls Chemical Co., Ltd.
m, Werk Huelg)'s ■Best Ray (Ve
Stolen) A Go-18) 1000g of the mixture in a glass flask on a roll gear table for 15 minutes.
Stir for a minute. The mixture was then extruded through two passes through a single screw extruder. The granules obtained in this way were put into an injection molding machine (Ailro e-molding machine).
und Aarburg) 200) to 220”C (
7) Heat to form into a plate and then heat to 180℃
After molding for 5 minutes. The molded article was colored an intense blue with excellent fastness.

0.6 g of the indanthrone blue pigment mixture obtained in Example 6 was mixed with 67 g of polyvinyl chloride, 33 g of dioctyl phthalate, 2 g of dibutyltin laurate and 2 g of titanium dioxide, and the mixture was heated at 160"C for 15 g. The PVC sheets were processed into sheets by roll milling for a minute.The resulting PVC sheets had a very intense blue color, which was robust to migration and light.

Branch m Polypropylene granules [Chemie
■Dub L/N (DAPLEN) from Linz)
PT-55) and 20 g of a 50% pigment preparation consisting of 10 g of the indanthrone blue pigment mixture obtained in Example 7 and 10 g of magnesium behenate are placed in a mixing drum and mixed well. The granules thus obtained were processed into filaments by melt spinning at 260-285°C. A blue filament with good light fastness and excellent fiber properties was obtained.

(A) 8 g of the indanthrone blue pigment mixture obtained in Example 4 and (B) titanium dioxide [Kronos Titanium Co., Ltd.]
KRONO9TITAN GmbH) Kronos (KR
Disperser mat (D
ISPERMAT) ■ (manufactured by Hediget, Baseldorf) was used to disperse well in a solution of the following composition: Cellulose acetobutyrate (25% solution in butyl acetate) 21.5 g Lyzirconium octonate 6 NUODEX ■)
1g Aromatic solvent (SOLVESSO 15G by Esso) 12g
Butyl acetate 17.5g xylene
13g.

After removing the glass beads, each of the two dispersions was mixed with a polyester resin [DYNAPOL]
H700 (55% solution), '1 DYNAMIT NOBEL) 24g
and melamine resin [MAPRENAL
) @ IF 850 (solution in 55, Hoechst)]
mixed with. Then this blue pigment varnish suspension 12.5
g was mixed with 45.0 g of white pigment varnish suspension. The pigment varnish thus obtained was spray applied to an aluminum plate and baked at 130°C. A clear topcoat of excellent gloss was obtained.

Claims (1)

[Claims] 1. a) Formula I ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Indanthrone blue pigment of (I) and b) Formula II ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [Formula In the middle, X^■ is H^■ or a group of formula (M^n^■)/n or N^■ (R) (R_1) (R_2) (R_3)
(where M is a monovalent, divalent or trivalent metal cation, n is a number of 1, 2 or 3, R, R^1, R^
2, R^3 are each independently hydrogen, C_1-C
_1_8-alkyl, C_5-C_6-cycloalkyl, phenyl, or phenyl substituted by C_1-C_1_8-alkyl, or R_2 and R_3 together with the nitrogen atom to which they are attached represent a pyrrolidine group, indazolidine , means a piperidine group, a piperazine group or a morpholine group, or R_1, R
_2, R_3 together with the nitrogen atom to which they are bonded mean a pyrrole group, pyridine group, picoline group, pyrazine group, quinoline group or isoquinoline group), and m is a numerical value from 0.5 to 2] and a sulfonated indanthrone blue derivative. 2. The composition according to claim 1, wherein m in the sulfonated indanthrone blue derivative of formula II is 1. 3. X^■ in the sulfonated indanthrone blue derivative of formula II has the formula (M^n^■)/n (where M^n^■ is an alkali metal cation or an alkaline earth metal cation, The composition according to claim 1, wherein n is 1 or 2. 4. The composition according to claim 3, wherein M^n^■ is a sodium ion or a calcium cation. 5. The composition according to claim 1, wherein the ratio of component (a) to component (b) is 99.8 to 90% by weight: 0.2 to 10.0% by weight.